Chapter 14 review 1 For the overall hypothetical reaction A + 5B → 4C, the rate of appearance of C given by Δ[C]/Δt is the same as A) Δ[A]/Δt B) -(5/4)(Δ[B]/Δt) C) -(4/5)(Δ[B]/Δt) D) -(1/4)(Δ[A]/Δt) E) none of the above. 2 When heated, the compound RX3 decomposes to a mixture of products. The following data were collected for the decomposition at 100º C. What is the average rate of reaction, -Δ [RX3]/Δt, over the entire experiment? A) B) C) D) E) 0.0028 mol/L.s 0.045 mol/L.s 0.0014 mol/L.s -0.0027 mol/L.s 0.0057 mol/L.s 3 The initial rate of the reaction PCl5 → PCl3 + Cl2 is increased a factor of four when the concentration of PCl5is doubled. Therefore, the rate A) depends on the concentrations of PCl3 and Cl2. B) is first order with respect to PCl5. C) is second order with respect to PCl5. D) is fourth order with respect to PCl5. E) is first order with respect to PCl3. 4 Bromine atoms react with iso-butane (iso-C4H10) to form hydrogen bromide and the tbutyl radical (t-C4H9): Br + iso-C4H10 → HBr + t-C4H9. The reaction is first order with respect to each of the reactants, and at 298 K, the rate constant is 1.02 x 106 L mol-1 s-1. Calculate the initial rate of the reaction in a 4.0 L reaction vessel containing 0.60 moles of iso-butane and 0.00010 moles of bromine atoms. A) 1.5 mol L-1 s-1 B) 3.8 mol L-1 s-1 C) 2.5 x 1011 mol L-1 s-1 D) 2.5 x 102 mol L-1 s-1 E) 6.7 x 102 mol L-1 s-1 1 5 Consider the thermal decomposition of cyclobutane (C4H8(g)) at 438º C, C4H8(g) → 2C2H4(g). The reaction follows first-order kinetics and the rate constant is k = 2.48 x 10-4 s-1. If the initial concentration of cyclobutane is 0.800 mol/L, what concentration will remain after 10.0 min? A) 0.689 mol/L B) 0.455 mol/L C) 0.333 mol/L D) 0.248 mol/L E) 0.0061 mol/L 6 A certain first-order reaction is 46 % complete in 68 min at 25°C. What is its rate constant? A) 9.1 x 10-3 min-1 B) 1.1 x 10-2 min-1 C) 31 min-1 D) 51 min-1 E) none of the above 7 Consider the reaction A → products. Which, if any, of the following plots is consistent with a second-order reaction? A) ln[A] plotted against time gives a straight line of positive slope. B) ln[A] plotted against time gives a straight line of negative slope. C) 1/[A] plotted against time gives a straight line of positive slope. D) 1/[A] plotted against time gives a straight line of negative slope. E) None of the above plots is consistent with a second-order reaction. 8 Consider the reaction A → products. Which of the following plots is consistent with a zero-order reaction? A) [A] plotted against time gives a horizontal, straight line. B) ln[A] plotted against time gives a straight line of negative slope. C) 1/[A] plotted against time gives a straight line of positive slope. D) [A] plotted against time gives a straight line of negative slope. E) [A] plotted against time gives a curved line of negative slope, decreasing in magnitude as time increases. 9 What is the value of the rate constant for a first-order reaction for which the half-life is 26.7 min? A) 18.5 min-1 B) 38.5 min-1 C) 9.25 min-1 D) 19.3 min-1 E) 0.0260 min-1 2 10 The rate constant of a first-order reaction is 3.68 x 10-2 s-1 at 150°C, and the activation energy is 71 kJ/mol. What is the value of the rate constant at 170°C? A) 9.2 x 10-2 s-1 B) 3.7 x 10-2 s-1 C) 2.49 s-1 D) 4.0 x 10-2 s-1 E) none of the above 11 In order to obtain the activation energy of a reaction using a graphical method, __________ is plotted against _________, giving a straight line whose slope is equal to __________. A) k; T; -Ea B) k; 1/T; -Ea C) lnk; T; -Ea/R D) k; 1/T; -Ea/R E) lnk; 1/T; -Ea/R 12 Select the appropriate rate law for the elementary process shown below. 2A → B + C A) Rate = k[2A] B) Rate = k[A] C) Rate = k[A]2 D) Rate = k[A]1/2 E) Rate = 2k[A] 13 The reaction 3ClO-(aq) → ClO3-(aq) + 2Cl-(aq) has been proposed to occur by the following mechanism. ClO-(aq) + ClO-( aq)→ ClO2-( aq) + Cl-( aq) (slow) ClO2-(aq) + ClO-(aq) → ClO3-(aq) + Cl-(aq) (fast Which rate law is consistent with this mechanism? A) rate = k[ClO-] B) rate = k[ClO-]3 C) rate = k[ClO2-][ClO-] D) rate = k[ClO-]2 E) rate = k[Cl-][ClO-]2 14 Consider the reaction: 2NO(g) + 2H2(g) → N2(g) + 2H2O(g) A suggested mechanism for this reaction follows: (1) NO(g) + NO(g) → N2O4(g) (slow) (2) N2O4(g) + H2(g) → N2(g) + H2O2 (g) (fast) (3) H2O2(g) + H2(g) → 2H2O(g) (fast) Based on this mechanism, which, if any, of the following actions will not affect the rate of the reaction? 3 A) B) C) D) E) adding a catalyst adding more NO(g) adding more H2(g) increasing the temperature All of these will affect the rate of the reaction. 15 A catalyst speeds up a reaction by A) increasing the number of high-energy molecules. B) increasing the temperature of the molecules in the reaction. C) increasing the number of collisions between molecules. D) increasing the activation energy for the reaction. E) providing a new reaction pathway for molecules. 16 Consider the reaction: CH3Cl(aq) + OH-(aq) → CH3OH(aq) + Cl-(aq) If the rate of appearance of CH3OH(aq) remains constant at 1.0 x 10-4 mol/(L·min), and the initial concentrations of both reactants are 0.10 mol/L, how long will it take to consume half of the reactants? A) 10,000 min B) 1,000 min C) 500 min D) 100 min E) none of the above 17 Consider the reaction 2A + 2B + C → 2D + E If the rate law for this reaction is Rate = k[A][B]2, what will be the effect on the rate if the concentrations of A, B and C are all doubled at the same time? A) The rate will increase by a factor of 2. B) The rate will increase by a factor of 4. C) The rate will increase by a factor of 6. D) The rate will increase by a factor of 8. E) More information is needed before this question can be answered. 18 Nitric oxide (NO) reacts with hydrogen (H2) according to the equation: 2NO(g) + 2H2(g) → N2(g) + 2H2O(g) The following initial rates of reaction have been measured for the given reactant concentrations. Which of the following is the rate law (rate equation) for this reaction? A) rate = k[NO]2 [H2] 4 B) C) D) E) rate = k[NO] [H2]2 rate = k[NO] [H2]4 rate = k[NO] [H2] rate = k[NO]1/2 [H2]1/4 19 The following initial rate data were collected for the reaction: 2A + B → C + D What is the value of the rate constant? A) k = 1.42 x 10-2 s-1 B) k = 2.83 x 10-3 L mol-1 s-1 C) k = 1.42 L2 mol-2 s-1 D) k = 0.532 x 10-3 L2 mol-2 s-1 E) k = 4.26 x 10-1 L mol-1 s-1 20 A solution of sucrose in water has an initial concentration of 0.155 mol/L. The sucrose is being converted to other sugars in a reaction which is first-order with respect to the sucrose concentration. Exactly 30 minutes later, the sucrose concentration has fallen to 0.131 mol/L. Calculate the value of the rate constant in s-1. A) 9.3 x 10-5 s-1 B) 4.1 x 10-5 s-1 C) 5.6 x 10-3 s-1 D) 1.7 x 10-1 s-1 E) none of the above 21 The reaction A → products is first-order with respect to A. Which of the following correctly describes a plot of rate data for this reaction? A) [A] plotted vs time gives a straight line of negative slope. B) [A] plotted vs time gives a straight line of positive slope. C) ln[A] plotted vs time gives a straight line of positive slope. D) ln[A] plotted vs time gives a straight line of negative slope. E) 1/[A] plotted vs time gives a straight line of positive slope. 22 Tetrafluoroethene (C2F4) dimerizes at 300º C to form octafluorocyclobutane (cycloC4F8) according to the equation 2C2F4(g) → cyclo-C4F8(g) The rate law for the reaction is: Rate = (0.080 L mol-1 min-1)[C2F4]2 In an experiment where the initial concentration of tetrafluoroethylene is 0.10 mol/L, what concentration remains after 700 min? 5 A) B) C) D) E) 8.0 X 10-3 mol/L 8.0 X 10-4 mol/L 2.8 X 10-3 mol/L 0.075 mol/L 0.015 mol/L 23 For the reaction A → products, the rate law is Rate = k[A]2. Starting with [A] = 0.100 mol/L, its concentration is found to be 0.0652 mol/L after 600. seconds. What is the value of the rate constant? A) 5.8 x 10-5 L . mol-1 .s-1 B) 7.1 x 10-4 L . mol-1 .s-1 C) 3.2 x 10-3 L . mol-1 .s-1 D) 8.9 x 10-3 L . mol-1 .s-1 E) none of the above 24 In an enzymatic fermentation, the initial concentration of sugar is 0.16 mol/L; after 10.0 hours the concentration is 0.080 mol/L; after 20.0 hours the concentration is 0.040 mol/L. What is the order of this reaction, and what is the rate constant? A) zero order; 1.67 x 10-6 s-1 B) first order; 1.93 x 10-5 s-1 C) first order; 1.67 x 10-6 s-1 D) second order; 3.71 x 10-10 s-1 E) second order; 1.67 x 10-6 s-1 25 From the following data, estimate the activation energy for the gas-phase reaction H2 + I2 → 2HI A) B) C) D) E) 21.0 kJ/mol 2.10 x 104 kJ/mol 1.75 x 102 kJ/mol 9.00 x 102 kJ/mol none of the above 26 A second-order rate constant is given by k = (6.5 x 107 L·mol-1·s-1)e-13500 K/T What is the the activation energy, Ea, for this reaction? A) 135 kJ/mol B) 56 kJ/mol C) 112 kJ/mol D) 162 kJ/mol E) 782 kJ/mol 6 27 The reaction of ethylene (C2H4) with butadiene (C4H6) to form cyclohexene (C6H10) has an activation energy (Ea) of 115 kJ/mol. The reverse reaction (decomposition of cyclohexene to ethylene and butadiene) has an activation energy of 287 kJ/mol. What is the heat of reaction, Δ Hrxn, for the forward reaction? A) +115 kJ/mol B) +287 kJ/mol C) -287 kJ/mol D) +172 kJ/mol E) -172 kJ/mol 28 Consider the following mechanism for the oxidation of bromide ions by hydrogen peroxide in aqueous acid solution. (1) H+ + H2O2 → H3O2+ (rapid equilibrium) (2) H3O2+ + Br- → HOBr + H2O (slow) (3) HOBr + H+ + Br- → Br2 + H2O (fast) What is the overall reaction equation for this process? A) 2H+ + H2O2 + Br- + HOBr → H3O2+ + Br2 + H2O B) H3O2+ + H+ + 2Br- → Br2 + 2H2O C) 2H+ + 2Br- + H2O2 → Br2 + 2H2O D) 2H3O2+ + 2Br- → H2O2 + Br2 + 2H2O E) none of the above 29 The mechanism for the gas-phase reaction 2NO + Cl2 → 2NOCl is suggested to be: (1) NO + NO → N2O4 (slow) (2) N2O4 + Cl2 → 2NOCl (fast) Based on this mechanism, the rate law for the overall reaction is: A) Rate = k [NO] B) Rate = k [NO]2 C) Rate = k [NO2]2[Cl2] D) Rate = k [Cl2] E) Rate = k [NO2]2[Cl2]2 30 At elevated temperatures in the gas phase, cyclopropane reacts to form propene. The rate of reaction is given by: rate = Δ[propene]/Δt = k[cyclopropane]. Which one of the following actions is least likely to cause a change in the rate of this reaction? A) adding a catalyst B) raising the temperature C) doubling the initial amount of cyclopropane D) halving the volume of the reaction vessel, but keeping the initial amount of cyclopropane constant. E) continuously removing propene as it is formed 7